Caoutchouc substance and process of making same.



I JNITED STATES rig grant]: OFFICE.

FRITZ HOFMANN ANID' CARL COUTELLE, OF ELIBERFELD, GERMANY, ASSIGNORS TO FARBENFABRIKEN voam. rnrnna. BAYER & C0,, or ELBERFELD, GERMANY, n

CORPORATION OF GERMANY.

' GAO' UTGHOUC SUBSTANCE PROCESS OF MAKING SAME.

No Drawing.

To all whom it may concern:

Be it known that we, FRITZ HOFMANN and CARL COUTELLE, doctors of philosophy, chemists, citizens of the German Empire, residing at Elberfeld, Germany, have invented new and useful Improvements in Caout chouc Substances and Processes of Making Same, of which the followingis a specification.

We have found that the hydrocarbon known as erythrene (divinyl):

the simplest hydrocarbon of the erythrene series, which series is characterized by containing the nucleus graphically represented C=C-C=C, can be converted by polymerization' into a new caoutchouc substance which mayreplace natural caoutchouc in its chemical and technical applications.

The process for producing the new caoutchouc substance consists in heating erythrene divinyl) in an appropriate manner So that the new caoutchouc substance is mainly produced. The process may also be carried out in the presence ofagents which promote polymerization or which act as diluents.

In order to illustrate our invention the following examples are given, the parts being by weight Example A: 500 parts of erythrene are dissolved in benzene and the resultingsolution is heated for 10 .hours in an autoclave to 150 C. The benzene and the lay-products which may have been formed, are distilled over with steam and the polymerization product in the form of an elastic substance remains behind.

Example B: 200 parts of erythrene are liquefied by cooling e. 91. with a mixture of ether and solid or liquid carbonic acid. The resulting liquid is then heated in an autoclave for four days at from 90100 C. Unchanged'erythrene is removed and the residue is heated for some time in oamw on the water bath, the temperature of which is finally brought to boiling. On distillation a liquid distils over, while the new product remains behind. s

Example C: 300 parts of erythrene are liquefied by cooling, 5 parts of acetic acid Specification of Letters Patent.

Application filed August 24, 1910. Serial No. 578,60 7.

Patented Aug. 12, 1913.

are added and the mixture is heated during2 days in an autoclave to 100 C. The new caoutchouc substance is isolated as above described.

Example D: 100 parts of erythrene are heated in an autoclave for some time e. 3 months in an incubator to about 35 C.

The new caoutchouc substance is isolated as above described. I

The new caoutchouc substance is a white substance insoluble in acetone. It swells up with chloroform or benzene to a white byaline substance from which the liquid can be poured oil. It is free from protein substances, which are alwayscontained in the natural caoutchouc and play an important part in it with regard to the elasticity of the natural caoutchouc. It forms ozonides, nitrosites, bromaddition products of which the following are the most characteristic: The nit-rosite is a light yellow powder decomposing at 150 to 155 0.. assuming a dark brown coloration; the ozonide is a thick colorless oil which pufis up on heating in the free flame and on being boiled with water it gives the peroxid of hydrogen reaction with bichromate of potassium or titanic acid and it is split into succinic acid and succinic aldehyde which latter substance gives a diphenylhydrazone melting at 125 0.

Our method of polymerization may-also be applied to mixtures of erythrene and hydrocarbons of the erythrene series and of similar groups in various proportions and the thus formed mixtures of new caoutchouc substances may be employed in the arts.

Ourv new caoutchouc substance described herein may be vulcanized, such vulcanized caoutchouc substances may be used in the same manner as vulcanized natural caoutchouc. We can also use a mixture of our new caoutchouc substance described herein with any other caoutchouc substance for example with those described in our other application Ser. No. 578,608 -filed August 24, 1910 and subject such mixtures to vulcanization, or we may mix our new caoutchouc sub-' stance with natural caoutchouc and subject this mixture to vulcanization. The vulcanized erythrene caoutchoucs are whitish to grayish products.

We claim 1. The process of producing a caoutchouclike substance from erythrene which comprises subjecting erythrene to caoutchoucforming conditions until a caoutchouc -like substance results insoluble in acetone.

2. The process of producing a caoutchouclike substance from erythrene which comprises heating erythrene under caoutchouc forming conditions until a product results insoluble in acetone.

chouc-like substance results insoluble in acelike substance from erythrene which com-- 3. The process of producing a caoutchouc-'- like substance which comprises polymerizing erythrene in the presence of an agent which promotes the polymerization until a caouttone.

4. The process of producing a caoutchouclike substance which comprises heating erythrene under caoutchouc forming condi-.

tions in the presence of an agent which promotes the polymerization until a caoutchouclike substance results insoluble in acetone.

5. The process of producing a caoutchouc prises heating erythrene under pressure until a caoutchouc-like substance results insoluble in acetone. 1

,6. The process of producing a caoutchouclike substance from erythrene which coin-- prises heating erythrene under pressurein: the presence of an agent which promotes the polymerization until a 'caoutchoucdike substance results insoluble in acetone. i'

7. The process of producing a caoutchouclike substance which comprises polymerizing erythrene 1n the presence of an agent of acid reaction until a caoutchouc-like substance re sults insoluble in acetone. I

' 8. The process of producing a caoutchouc like substance which comprises heating erythrene under caoutchouc forming conditions in the presence of an agent'of acid reaction until a caoutchouc-like substancere-.

sults insoluble in acetone.

9. The process of producing a caoutchouclike substance which comprises polymerizing erythrene in the presence of an acid untila caoutchouc-like substance results insolublein acetone. 7

'10. The process of producing a caoutchouclike substance which comprises heating erythrene under caoutchouc forming conditions in the presence of -an acid until'a' caoutchouc-like substance results insoluble-in acetone l 11. The process of producing a caoutchouclike' substance which comprises polymerizing erythrene in the presence of an organic acid until a caoutchouc-like substance resultsinsoluble in acetone.

12. The process of producing-a caoutchouclike substance which comprises heating erythrene under caoutchouc forming conditions in the presence of an organic acid until a caoutchouc-like substance results insoluble in acetone.

13. The process of producing a caoutchouc like substance which comprises polymerizing erythrene in the presence of an alifatic acid until a caoutchouc-like substance results insoluble in acetone.

14. The process of producing a caoutchouclike substance which comprises heating erythrene under caoutchouc forming conditions in the presence of an alifatic acid until a caoutchouc-like substance results insoluble in acetone.

- 15. The process of producing a caoutchouclike substance which comprises polymerizing erythrene under caoutchouc forming conditions in the presence of acetic acid until a caoutchouc-like substance results insoluble 1n acetone.

16. The process of producing a caoutchouclike substance which comprises heating erythrene in the presence of acetic acid until a caoutchouc-like substance results insolub e in acetone. I

17. The process-of producing a caoutchouclike substance [which comprises adding to erythrene a liquid diluent, and polyinerizing until a caoutchouc-like substance results insoluble in acetone.

' 18.- The process of roducingacaoutchouw like substance whic comprises adding to erythrene a liquid diluent and heating until a caoutchouc like I substance results insoluble in acetone.

1-9. The process of. pro ucing a caoutchouclike substance which 0 mprises adding to erythrene a liquid dilue t, polymerizing the tionsuntil acaoutchouc-like substance re sults insoluble in acetone, and separating the resulting caoutchouc-like substance from the by-products of the polymerization product.

' '22. The process of producing a caoutchouclike substance which comprises pol merizing erythrene under caoutchoucorming' conditions untila' caoutchouc-hke substance results msoluble in acetone, and separatingthe volatile constituents from the resulting product by distillation.

23. The process of lproducing a caoutchouclike substance whic comprises polymeriz ing erythrene by heating under caoutchouc forming conditions until a caoutchouc-like substance results insoluble in acetone' and separating the volatile constituents from the resulting product b distillation with steam.

24:. The process 0 producing a'caoutchouclike substance which comprises polymerizing an erythrene hydrocarbon under caoutchouc forming conditions until a caoutchouc-like substance results insoluble in acetone and separating the volatile constituents from the resulting product b distillation with steam.

25. The process 0 producing a caoutchouc like substance which comprises heating an erythrene hydrocarbon under caoutchouc forming conditions until a caoutchouc-like substance results insoluble in acetone, and separating the volatile constituents from the resulting product by distillation with steam.

26. As anew product a caoutohouc-like substance comprising erythrene caoutchouc.

27. As a new product erythrene caoutchouc, being apolymerization product of erythrene which caoutchouc forms an ozonid which yields upon decomposition with water, succinic aldehyde among its decomposition products.

I 28. As a new product a caoutchouc-like substance comprising a caoutchouc-like polymerization product of an erythrene hydrocarbon the ratio of carbon to hydro en in such caoutchouc being greater than t atin isoprene caoutchouc.

29. New caoutchouc substances comprising erythrene caoutchouc obtained by polymerization of erythrene which are characterized by being whitish substances the color of which does not change, swelling up with chloroform to whitish hyaline sub-- stances, and forming nitrosites and ozonids which'are thick O1lS being decomposed on being heated, which new caoutchouc substances in the vulcanized form are whitishto grayish products which are not adhesive FRITZ HOFMANN. [L.s.] CARL COUTELLE. as

' Witnesses:

CHAs. J. WRIGHT, ALFRED HENKEL. 

